CN1351129A - Process for refining and coverting residual oil - Google Patents
Process for refining and coverting residual oil Download PDFInfo
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- CN1351129A CN1351129A CN 00123135 CN00123135A CN1351129A CN 1351129 A CN1351129 A CN 1351129A CN 00123135 CN00123135 CN 00123135 CN 00123135 A CN00123135 A CN 00123135A CN 1351129 A CN1351129 A CN 1351129A
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Abstract
A process for refining and converting residual oil features that the residual oil with low contents of metal, colloid and asphalt is directly hydrogenated and the residual oil with high contents of metal, colloid and asphalt is first added to the equipment to remove asphalt and then hydrogenated. Its advantages include high power to process raw oil, low output rate of coke and cracked gas, high conversion rate and long service life of catalyst.
Description
The present invention relates to the refining and method for transformation of residual oil.In particular, relate to utilize combination process to carry out the method for residual oil-refining and conversion.Combination process of the present invention is the reasonable associating of atmospheric and vacuum distillation, residual hydrogenation, catalytic cracking and solvent deasphalting technology, be characterized in to handle heavy and inferior feedstock oil, and in low coke yield and gas yield, high gasoline and diesel yield, do not increasing the residual oil processing power under the expansion instrument volumetrical condition.
Usually, residual oil such as normal pressure residual oil or vacuum residuum contain quite a lot of not distillable high-molecular weight compounds.Such compound contains nonhydrocarbon condensed ring material and heavy metals such as Ni, V such as a large amount of colloids, bituminous matter.If such residual oil is made the raw material of device such as catalytic cracking or hydrocracking, contained metal (Ni, V etc.) can be deposited in the activity of such catalysts in the heart in the charging so, makes rapid catalyst deactivation.In addition, a large amount of colloid, the quick coking and deactivation that bituminous matter also can cause catalyzer.Therefore for fear of the rapid deactivation of above-mentioned catalyzer, resid feed enters before the said apparatus, should remove its metal, colloid and bituminous matter.
In order to achieve the above object, a kind of method has been described among the CN1117071A, this method is that residual oil raw material carries out diasphaltene earlier, obtain pitch fractions and deasphalted oil, in the presence of hydrogen, deasphalted oil is by the catalyst for demetalation bed, obtain the deasphalted oil of upgrading, deasphalted oil behind the upgrading and one or more flash distillation fraction oil distillate fusion, the blended oil of generation carries out hydrocracking again, to produce one or more fraction oil distillates.This method is better to the residual oil raw material of handling single character, if handle the residual oil raw material of two kinds of different in kinds simultaneously, then can influence fraction oil yield or increase the solvent that diasphaltene is used.Because enlarging crude charging capacity at present is a kind of effective means that refinery obtains higher economic benefit.Along with the internationalization in crude oil market, what refinery was processed no longer is single crude oil, but diversified crude oil.As a result, the oil property of processing alternates betwwen good and bad, and character heavy, residual oil also is excellent, bad difference.If the method for describing with above-mentioned patent again, two kinds of excellent, bad different stock oil hybrid process are carried out solvent deasphalting processing jointly, and stock oil of different nature is interacted, and cause deficiencies such as processing charges raising, actual deasphalted oil yield be low.
Purpose of the present invention remedies above-mentioned deficiency exactly, when expansion processes raw material oil product kind scope and treatment capacity, still can high efficiency processing different material oil, and obtain higher liquid yield simultaneously.
Specific embodiments of the present invention comprises the steps:
(1) difference of based on crude character, crude oil enters the different tripping device of two covers respectively with more bad crude oil preferably, crude oil is preferably told distillate and the atmospheric residue or the vacuum residuum of gas, different boiling ranges scope, and more bad crude oil is told the distillate and the vacuum residuum of gas, different boiling ranges scope;
(2) vacuum residuum of being told by more bad crude oil in the step (1) deasphalting unit that desolvates carries out solvent deasphalting, deasphalted oil and de-oiled asphalt;
(3) deasphalted oil in the step (2) enters hydrogenation unit and carries out hydrotreatment, and the hydrogenation resultant enters gas-liquid separator, isolates hydrogen-rich gas and liquid phase and generates oil, and liquid phase generates oil and delivers to atmospheric tower, reclaims light ends and hydrogenation long residuum by this tower;
(4) the hydrogenation long residuum in the step (3) goes catalytic cracking unit to carry out lighting;
Better crude oil described in the step (1) is meant that its vacuum residuum can satisfy the crude oil that hydrogenation technique device described in the step (3) requires feed properties, and described more bad crude oil is meant that its vacuum residuum can not satisfy the crude oil that the described hydrogenation technique device of step (3) requires feed properties.Described feed properties requires mainly to be meant the restriction to metal, colloid and bituminous matter equal size; Described hydrogenation technique device is relevant with concrete hydrogenation technique to the index request of feed properties, for example: the Ni+V amount is not more than 150 μ g/g in the charging of the suitable processing of fixed bed hydrogenation technology at present, and the moving-bed hydrogenation technique can be processed the charging of Ni+V amount greater than 150 μ g/g.
Tripping device in the described step (1) generally is atmospheric fractional tower and vacuum fractionation tower.Described crude oil preferably according to the different requirements of refinery, can be provided with vacuum distillation tower behind the distillate (as vapour, coal, diesel oil etc.) of isolating gas, different boiling ranges scope through atmospheric fractional tower, atmospheric residue, also vacuum distillation tower can be set.For example want the lubricated wet goods non-fuel product of the vacuum gas oil production that goes out with the atmospheric residue decompression separation, then vacuum distillation tower must be set, isolate vacuum distillate and vacuum residuum.Described more bad crude oil is after separating through normal pressure, tell the distillate (as vapour, coal, diesel oil etc.) of gas, different boiling ranges scope, in order to reduce the consumption of solvent in the solvent deasphalting unit described in the present invention (2) step, improve the efficient of solvent deasphalting unit, vacuum distillation tower must be set, tell vacuum distillate and vacuum residuum.
Atmospheric residue of being told by crude oil preferably in the described step (1) or vacuum residuum can directly or with the vacuum distillate fusion enter catalytic cracking unit or other catalytic cracking unit described in the present invention (4) step, but the present invention preferentially recommends this part oil to enter hydrotreater described in the present invention (3) step.
In the atmospheric tower fractionation of step (1) and step (4), the cut point that generally guarantees long residuum is 300-400 ℃, preferably about 340-380 ℃.Could guarantee like this gasoline fraction in the logistics and diesel oil distillate are told, and be sent into corresponding oil product jar or downstream processing unit (plant) respectively.
In the vacuum distillation tower fractionation of step (1), the cut point that generally will guarantee vacuum residuum is 450-600 ℃, preferably about 500-550 ℃.Could guarantee like this vacuum gas oil fraction in the long residuum is told.Better crude oil is after separating through normal pressure, if entering vacuum distillation tower again separates, the raw material that the vacuum gas oil of telling can directly be produced lubricating oil as the raw material or the work of hydrocracking, catalytic cracking unit also can be done the fusion charging of hydrogenation reaction section of the present invention.The present invention is most preferably with the charging of described catalytic cracking unit of its work (4) step or the charging of other catalytic cracking unit; By the raw material that the vacuum gas oil of more bad crude production can directly be produced lubricating oil as the raw material or the work of hydrocracking, catalytic cracking unit, also can do the fusion charging of hydrogenation reaction section of the present invention.The present invention preferably does it fusion charging of hydrogenation reaction section of the present invention, most preferably it is done the charging of the present invention (4) described catalytic cracking unit of step or other catalytic cracking unit.
The solvent deasphalting technology can be used rotating disk contact tower or tray column described in the step (2).Hydrocarbon oil feed enters from the top, and extraction solvent enters from the bottom.The extraction medium that is adopted normally contains the light hydrocarbon solvent of alkane compound.The alkane compound that commerce provides comprises C
3～C
8Alkane is as propane, butane, Trimethylmethane, pentane, iso-pentane, hexane or two or more mixture wherein.For purposes of the invention, C preferably
3～C
7Alkane, most preferably butane, pentane or its mixing.Operational condition is generally: total extraction solvent and hydrocarbon-type oil weight ratio are 1.5～8, and pressure is 0.1～5.0Mpa, and temperature is 60～250 ℃.The deasphalted oil of being told enters the hydrogenation reaction section in the present invention (3) step and carries out hydrotreatment, and de-oiled asphalt can remove to do the bituminous blend component, can defocusing, also can go hydrogen manufacturing, and the hydrogen of gained can be used hydrogenation reaction section of the present invention.
The hydrogen-rich gas that the described hydrotreatment process of step (3) produces can return hydrogenator after washing, purification continues to use, the light ends fractionation that liquid phase generates oil generation after normal pressure separates mainly is meant vapour, diesel oil etc., and product jar or downstream processing unit (plant) can deoil.Described hydrotreatment technology can be any technology of the present invention that is applicable to, as fixed bed weight, residual hydrogenation technology, suspension bed weight, residual hydrogenation technology, ebullated bed weight, residual hydrogenation technology, expanded bed weight, residual hydrogenation technology, heavy, the residual hydrogenation technology of moving-bed., residual hydrogenation technology heavy with at present industrial more ripe fixed bed is example, and the heavy residual oil hydrocatalyst of employing is meant the single catalyst or the combination catalyst of functions such as having weight, residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking.These catalyzer generally all are to be carrier with porous refractory inorganic oxides such as aluminum oxide, the oxide compound of group vib and/or VIII family metal such as W, Mo, Co, Ni etc. is an active ingredient, the catalyzer that optionally adds other various auxiliary agents such as P, Si, elements such as F, B, for example CEN, the FZC series of being produced by Fushun Petrochemical Research Institute pilot scale base weighs, residuum hydrogenating and metal-eliminating catalyst, and ZTN, the ZTS catalyst series produced by first fertilizer plant of Qilu Petrochemical company just belong to this class catalyzer.At present in fixed bed residual hydrogenation technology, it often is the supporting use of multiple catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst, hydrocracking catalyst are wherein arranged, according to the specific requirement of product or the material of raw material, sometimes can not adorn hydrodenitrogenation catalyst or hydrocracking catalyst etc., the filling order generally is that stock oil is contacted with hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, hydrocracking catalyst successively.Technology with these several catalyst mix fillings is also arranged certainly.Described hydrotreatment reaction conditions is: reaction pressure is 5-35MPa, and 10-20Mpa, the about 300-500 of temperature ℃ often often is 350-450 ℃.Volume space velocity and hydrogen dividing potential drop are to select according to the characteristic for the treatment of material and the transformation efficiency and the refining depth of requirement during liquid.Often volume space velocity is in about 0.1-5.0h during liquid
-1, preferably at 0.15-2h
-1Between scope in.Hydrogen to oil volume ratio is 100-5000,500-3000 often.
Can obtain a kind of gas fraction, a kind of gasoline fraction, a kind of gas oil fraction and a kind of slurry oil behind the catalytic cracking reaction in the described step (5), wherein gas fraction mainly contains stable hydrocarbon and the unsaturated hydrocarbons (as methane, ethane, propane, butane, ethene, propylene, butylene etc.) of C1-C4.
The feed properties of catalytic cracking unit should be able to satisfy the requirement of catalytic cracking unit to each index of charging in the described step (5), and the index required as present catalytic cracking unit charging is: (1) sulphur content is not higher than 0.35w%-0.6w%; (2) Conradson carbon residue is less than 5w%-10w%; (3) heavy metal nickel and vanadium total content are not higher than 20-45 μ g/g; (4) the total nitrogen content general requirement is less than 0.35w%, or basic n content is less than 0.15w%.If the index of catalytic cracking unit charging surpasses above-mentioned restriction, the then easy inactivation of catalytic cracking catalyst, and gas, coke yield increase in the product; Productive rate such as gasoline, diesel oil reduces.If the character of the normal slag of hydrogenation can not satisfy above-mentioned catalytic cracking charging index, then can mix the vacuum distillate in the step of the present invention (1) or the vacuum distillate of other device, or the operating severity that increases the hydrogenation reaction section satisfies index etc.The gas that catalytic cracking unit the generates body recovery system of can degassing, gasoline fraction is preferably all delivered to the oil product jar.Gas oil often is sent to the further hydrotreatment of downstream hydrofining section at least in part, and slurry oil is generally after the suspension fine particle that it contains is separated, can deliver to step (5) catalytic cracking unit import, again carry out catalytic cracking, also can deliver to the solvent deasphalting unit of step (2), can also deliver to hydrogenation reaction system of the present invention and mix with hydrogenating materials and carry out hydrogenation jointly, the present invention delivers to hydrogenation reaction system of the present invention to mix with hydrogenating materials and carry out hydrogenation jointly.Reason is to contain a large amount of arenes in the slurry oil of catalytic cracking, condensed-nuclei aromaticss such as bituminous matter in residual oil raw material and the hydrogenated products had solvability preferably, in hydrogenation process, the condensed-nuclei aromaticss such as bituminous matter that can reduce or eliminate in residual oil raw material and the hydrogenated products take place to assemble and the probability of coking, make residual hydrogenation equipment handle the worse residual oil of more character, and can also reduce sedimentation of coke amount on the hydrogenation catalyst, prolong the work-ing life of catalyzer, residual hydrogenation equipment can be turned round under higher transformation efficiency.The operational condition of catalytic cracking unit is generally: temperature is 450～600 ℃, preferably 460～550 ℃; The agent weight of oil is than 2～30, and preferably 2～20; With 0.1～15 second duration of contact of catalyzer, best 0.5～5 second; Pressure 0.1～0.5Mpa.The catalytic cracking catalyst that is adopted comprises the catalyzer that is generally used for catalytic cracking, as silica-alumina catalyst, silica-magnesia catalyst, acid-treated carclazyte and X type, Y type, ZSM-5, M type, layer post equimolecular sieve cracking catalyst, molecular sieve cracking catalyst preferably, this is because the active height of molecular sieve cracking catalyst, green coke is few, gasoline yield height, transformation efficiency height.The reactor of described catalytic cracking unit can be the catalyst cracker of various types, and preferably riser reactor or riser tube add the bed reactor.Technical process is generally: stock oil injects from the riser reactor bottom, contact with high temperature catalyst from the fresh regenerated of revivifier, the oil gas that cracking reaction generates and the catalyst mixture of deposit coke move up along riser reactor, finish the catalytic cracking reaction of whole stock oil.
The present invention is applicable to normal slag and the hydrocracking that subtracts slag, is particularly useful for the poor residuum hydrocracking of high metal, high carbon residue, high condensed ring material, high nitrogen-containing.
Compared with prior art, the present invention has been owing to adopted the stage treatment of residual oil, i.e. metal and colloid, the less direct slag input oil of the residual oil hydrogenation unit of bituminous matter equal size; Metal and colloid, the more advanced solvent deasphalting unit of residual oil of bituminous matter equal size, deasphalted oil slag input oil hydrogenation unit, the result has not only increased the stock oil treatment capacity, but also the corresponding device operating severity that reduced.In addition, organically combine with catalytic cracking again, both improved the processing power of catalytic cracking unit, reduced coke and reacted gas productive rate again, but also prolonged the running life of residual hydrogenation equipment catalyzer, realized the high conversion of residual oil.
Fig. 1 is the simple and easy schematic flow sheet of the embodiment of the invention, and Fig. 2 is a comparative example schematic flow sheet of the present invention.
Below in conjunction with drawings and Examples the present invention is described in further details.
As shown in Figure 1, stock oil 25 enters atmospheric and vacuum distillation unit 30 preferably, fractionates out gas 26, gasoline 27, diesel oil 28, vacuum gas oil 34 and long residuum 32, and wherein gas 26, gasoline 27, diesel oil 28 go out device; More bad stock oil 24 enters atmospheric and vacuum distillation unit 31, fractionate out gas 12, gasoline 13, diesel oil 14, vacuum gas oil 19 and vacuum residuum 33, wherein gas 12, gasoline 13, diesel oil 14 go out device, vacuum residuum 33 directly enters solvent extraction device 21, obtains deasphalted oil 29 and de-oiled asphalt 23.Deasphalted oil 29, vacuum residuum 32 enters residue fixed-bed hydrotreater 2 with the charging 1 that hydrogen is formed, the resultant of reaction 3 of gained enters resultant separator 4, the hydrogen-rich gas 5 that obtains, can return hydrogenation unit after purifying recycles, the product liquid 6 that obtains enters atmospheric fractional tower 7, the gas 8 that fractionation obtains, gasoline 10 and diesel oil distillate 9 go out device, long residuum 11 at the bottom of the tower, vacuum gas oil 34 is mixed into catalytic cracking unit 15 with vacuum gas oil 19 and carries out cracking, the gas 16 that catalytic cracking reaction generates, gasoline 17, diesel oil 18 and catalytically cracked oil 22 go out device, catalytically cracked oil 22 in the present embodiment is for once passing through, do not return hydrogenation unit, calculate by unconverted oil during material balance.
As shown in Figure 2, the charging 1 that stock oil and hydrogen are formed enters residue fixed-bed hydrotreater 2, the resultant of reaction 3 of gained enters resultant separator 4, the hydrogen-rich gas 5 that obtains, can return hydrogenation unit after purifying recycles, the product liquid 6 that obtains enters atmospheric fractional tower 7, the gas 8 that fractionation obtains, gasoline 10 and diesel oil distillate 9 go out device, long residuum 11 directly enters catalytic cracking unit 15 and carries out cracking at the bottom of the tower, the gas 16 that catalytic cracking reaction generates, gasoline 17, diesel oil 18 and catalytically cracked oil 22 go out device, catalytically cracked oil 22 does not carry out other conversions again, calculates by unconverted oil during material balance.
Following embodiment has illustrated the present invention and has not limited its scope.
Embodiment
On small-sized lifting tubular type catalytic cracking unit, mix pilot scale residual hydrocracking device and solvent extraction device and atmospheric and vacuum distillation unit and test.The residue fixed-bed hydrogenation catalyst that uses in following test is heavy, the residuum hydrogenating and metal-eliminating catalyst of being produced by Fushun Petrochemical Research Institute pilot scale base of CEN, FZC series, by ZTN, ZTS series weight, residual hydrogenation denitrogenation, the desulfurization catalyst of first fertilizer plant of Qilu Petrochemical company production.The order of catalyst loading is hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrogenation catalyst.The Hydrodemetalation catalyst that uses in this test is CEN-5, CEN-6; Protective material is CEN-2, CEN-4, FZC-16 (over current protection agent); Hydrobon catalyst ZTS-01, ZTS-02, ZTS-03; Hydrodenitrogenation catalyst ZTN-01.Filling ratio between each catalyzer is:
CEN-2∶FZC-16∶CEN-4∶CEN-5∶CEN-6∶ZTS-01∶ZTS-02∶ZTS-03∶ZTN-01＝1∶1.25∶1.5∶2.62∶7.8∶6.63∶0.69∶0.87∶11(V/V)。
The solvent that the solvent extraction device uses is the mixture (1: 1, volume ratio) of butane, pentane.The employed catalyzer of catalytic cracking unit is RHZ200 (Qilu Petrochemical company of China Petrochemical Corporation catalyst plant is produced).
This test crude oil work flow is referring to Fig. 1, stock oil 1 and 2 passes through atmospheric and vacuum distillation at first respectively, the character of vacuum residuum and the character of vacuum gas oil are listed in table 1 respectively, wherein stock oil 1 is stock oil preferably, stock oil 2 is more bad stock oil, following vacuum residuum 1 is that stock oil 1 obtains through separating with vacuum gas oil 1, and vacuum residuum 2 is that stock oil 2 obtains through separating with vacuum gas oil 2.
Table 1 vacuum residuum character
| Vacuum residuum | ??????1 | ?????2 |
| Density (20 ℃), g/cm 3 | ????0.998 | ????1.0266 |
| Elementary composition | ||
| S，w％ | ????2.52 | ????5.40 |
| N，w％ | ????0.8 | ????0.40 |
| Carbon residue, w% | ????15.6 | ????23.9 |
| Ni，μg/g | ????48.0 | ????47.0 |
| V，μg/g | ????2.2 | ????152.0 |
Table 2 vacuum gas oil character
| Vacuum gas oil | ??????1 | ??????2 |
| Density (20 ℃), g/cm 3 | ????0.9094 | ????0.9389 |
| Elementary composition | ||
| S，w％ | ????1.13 | ????2.87 |
| N，w％ | ????0.17 | ????0.12 |
| Carbon residue, w% | ????0.09 | ????0.16 |
| Ni+V，μg/g | ????0.22 | ????0.45 |
Temperature: 200 ℃ of pressure: 1.0Mpa solvent ratio: 5 (V/V)
The result of vacuum residuum 2 solvent extractions is:
Deasphalted oil yield: 81.5w%, de-oiled asphalt: 18.5w%
Hydrotreatment is carried out in the deasphalted oil of vacuum residuum 1+ vacuum residuum 2, and the operational condition of fixed bed hydrogenation is as follows:
Temperature: 393 ℃ of pressure: the 15.4Mpa hydrogen-oil ratio, (V/V): 758
Air speed: 0.30h
-1Recycle hydrogen purity: 95V%
The liquid efflunent of reactor enters atmospheric tower and carries out the normal pressure fractionation, and the character of the productive rate of hydrogenated products and hydrogenation long residuum sees Table 3.
Table 3 residual hydrocracking result
| Sequence number | Data |
| Residue fixed-bed hydrogenated products productive rate, % | |
| H 2S+NH 3+ loss | ?????????????2.96 |
| C 1～C 4/ petroleum naphtha/diesel oil | ????????1.97/2.80/11.22 |
| The normal slag of hydrogenation | ?????????????82.55 |
| The normal slag of hydrogenation | |
| S/N，μg/g | ?????????????0.46/0.12 |
| Carbon residue/Ni+V, w%/μ g/g | ?????????????5.48/11.7 |
This test is that the mixing oil of the normal slag+vacuum gas oil 2 of vacuum gas oil 1+ hydrogenation carries out catalytic cracking, and the operational condition of catalytic cracking unit is:
Temperature: 502 ℃ of pressure: the 0.14Mpa agent-oil ratio, (W): 5.5
Finish duration of contact: 1 second
The reaction result of catalytic cracking sees Table 4.
Table 4 catalytic cracking reaction result
| Product distributes | |
| Dry gas, w% | ????3.75 |
| Liquefied gas, w% | ????2.40 |
| Gasoline, w% | ????49.15 |
| Diesel oil, w% | ????32.24 |
| Slurry oil, w% | ????6.24 |
| Coke, w% | ????5.22 |
The product of combination process process residual oils of the present invention distributes and sees Table 5.
Table 5 residual oil product processed of the present invention distributes
| Raw material, w% | |
| Crude oil 1 | ????50 |
| | ????50 |
| Hydrogen | ????0.30 |
| Product, w% | |
| H 2S+NH 3+ loss | ????0.59 |
| Dry gas | ????1.84 |
| Liquefied gas | ????1.99 |
| C 5～350℃ | ????88.96 |
| Heavy distillate, | ????2.53 |
| Coke, | ????2.20 |
| De-oiled asphalt | ????2.19 |
Comparative example
This tests the same embodiment of used crude oil, and two kinds of crude oil at first mix and pass through atmospheric and vacuum distillation again, and the character of vacuum residuum and the character of vacuum gas oil are listed in table 6, table 7 respectively.
Table 6 vacuum residuum character
| Density (20 ℃), g/cm 3 | ????1.01 |
| Elementary composition | |
| S，w％ | ????4.08 |
| N，w％ | ????0.62 |
| Carbon residue, w% | ????21.0 |
| Ni，μg/g | ????47.6 |
| V，μg/g | ????82.2 |
Table 7 vacuum gas oil character
| Density (20 ℃), g/cm 3 | ????0.922 |
| Elementary composition | |
| S，w％ | ????1.91 |
| N，w％ | ????0.25 |
| Carbon residue, w% | ????0.23 |
| Ni+V，μg/g | ????1.98 |
Vacuum residuum carries out hydrotreatment, the same embodiment of hydrogenation catalyst of fixed bed hydrogenation device filling, and the device operational condition is as follows:
Temperature: 393 ℃ of pressure: the 15.4Mpa hydrogen-oil ratio, (V/V): 758
Air speed: 0.30h
-1Recycle hydrogen purity: 95V%
The liquid efflunent of reactor enters atmospheric tower and carries out the normal pressure fractionation, and the character of the productive rate of hydrogenated products and hydrogenation long residuum sees Table 8.
Table 8 residual hydrocracking result
| Sequence number | Data |
| Residue fixed-bed hydrogenated products productive rate, % | |
| H 2S+NH 3+ loss | ??????????3.07 |
| C 1～C 4/ petroleum naphtha/diesel oil | ????1.16/1.24/8.83 |
| Long residuum | ??????????87.35 |
| The normal slag of hydrogenation | |
| S/N，μg/g | ???????0.58/0.11 |
| Carbon residue/Ni+V, w%/μ g/g | ???????6.89/25.9 |
The normal slag of hydrogenation directly carries out catalytic cracking, the same embodiment of catalyzer that catalytic cracking unit is used, and the device operational condition is:
Temperature: 502 ℃ of pressure: the 0.14Mpa agent-oil ratio, (W): 5.5
Finish duration of contact: 1 second
The reaction result of catalytic cracking sees Table 9.
Table 9 catalytic cracking reaction result
| Product distributes | |
| Dry gas, w% | ????4.22 |
| Liquefied gas, w% | ????5.40 |
| Gasoline, w% | ????47.17 |
| Diesel oil, w% | ????23.60 |
| Slurry oil, w% | ????9.4 |
| Coke, w% | ????10.21 |
The product of comparative example process residual oils distributes and sees Table 10.
Table 10 comparative example residual oil product processed distributes
| Raw material, w% | |
| Crude oil 1 | ????50 |
| | ????50 |
| Hydrogen | ????0.32 |
| Product, w% | |
| H 2S+NH 3+ loss | ????1.09 |
| Dry gas | ????3.37 |
| Liquefied gas | ????3.21 |
| C 5～350℃ | ????83.49 |
| Heavy distillate, | ????4.39 |
| Coke, | ????4.77 |
By table 5 and table 10 as can be seen the light oil yield of combination process of the present invention exceed 5.47% than the light oil yield of the existing technology in the comparative example, and the yield of heavy fraction oil and coke is low respectively by 1.86% and 2.57%, and unconverted oil (comprising de-oiled asphalt) also hangs down 2.24%.If present embodiment adopts catalytically cracked oil of the present invention to return the further hydrocracking scheme of hydrogenation system, the yield of light oil among the embodiment will be higher, and the yield of coke also can be lower.
Claims (20)
1, a kind of residual oil-refining and method for transformation comprise:
(1) difference of based on crude character, crude oil enters the different tripping device of two covers respectively with more bad crude oil preferably, crude oil is preferably told distillate and the atmospheric residue or the vacuum residuum of gas, different boiling ranges scope, and more bad crude oil is told the distillate and the vacuum residuum of gas, different boiling range scopes;
(2) vacuum residuum of being told by more bad crude oil in the step (1) deasphalting unit that desolvates carries out solvent deasphalting, deasphalted oil and de-oiled asphalt;
(3) deasphalted oil in the step (2) enters hydrogenation unit and carries out hydrotreatment, and the hydrogenation resultant enters gas-liquid separator, isolates hydrogen-rich gas and liquid phase and generates oil, and liquid phase generates oil and delivers to atmospheric tower, reclaims light ends and hydrogenation long residuum by this tower;
(4) the hydrogenation long residuum in the step (3) goes catalytic cracking unit to carry out lighting;
Better crude oil described in the step (1) is meant that the vacuum residuum that obtains after it separates can satisfy the crude oil that hydrogenation technique device described in the step (3) requires feed properties, and described more bad crude oil is meant that its vacuum residuum can not satisfy the crude oil that the described hydrogenation technique device of step (3) requires feed properties.
2, according to described residual oil-refining of claim 1 and method for transformation, after it is characterized in that described in the step (1) that crude oil is preferably at first isolated the distillate, atmospheric residue of gas, different boiling ranges scope through atmospheric fractional tower, described atmospheric residue also will enter the vacuum fractionation tower, isolates vacuum gas oil and vacuum residuum.
3,, it is characterized in that described in the step (1) that crude oil only enters atmospheric fractional tower preferably to isolate gas, the distillate of different boiling ranges scope, atmospheric residue according to described residual oil-refining of claim 1 and method for transformation.
4, according to described residual oil-refining of claim 1 and method for transformation, after it is characterized in that crude oil more bad described in the step (1) at first enters atmospheric fractional tower and isolates the distillate of gas, different boiling ranges scope, atmospheric residue, described atmospheric residue enters the vacuum fractionation tower again and isolates vacuum gas oil and vacuum residuum.
5,, it is characterized in that at the described atmospheric residue of step (1) and the described hydrogenation long residuum of step (3) be boiling range greater than 300-400 ℃ heavy oil or residual oil according to described residual oil-refining of claim 1 and method for transformation.
6,, it is characterized in that at the described atmospheric residue of step (1) and the described hydrogenation long residuum of step (3) be boiling range greater than 340-380 ℃ heavy oil or residual oil according to described residual oil-refining of claim 1 and method for transformation.
7,, it is characterized in that described vacuum residuum is boiling range greater than 450-600 ℃ residual oil according to claim 1 or 2 described residual oil-refining and method for transformation.
8,, it is characterized in that described vacuum residuum is boiling range greater than 500-550 ℃ residual oil according to claim 1 or 2 described residual oil-refining and method for transformation.
9, according to described residual oil-refining of claim 1 and method for transformation, it is characterized in that the solvent deasphalting in the described step (2) is to use rotating disk contact tower or tray column to handle, hydrocarbon oil feed enters from the top, and extraction solvent enters from the bottom, the extraction medium that is adopted is the light hydrocarbon solvent that contains alkane compound, operational condition is: total extraction solvent and hydrocarbon-type oil weight ratio are 1.5～8, and pressure is 0.1～5.0Mpa, and temperature is 60～250 ℃.
10,, it is characterized in that the extraction medium that the solvent deasphalting technology in the described step (2) adopts is C according to described residual oil-refining of claim 1 and method for transformation
3～C
7Alkane.
11,, it is characterized in that the extraction medium that the solvent deasphalting technology in the described step (2) adopts is butane, pentane or its mixture according to described residual oil-refining of claim 1 and method for transformation.
12, according to described residual oil-refining of claim 1 and method for transformation, it is characterized in that the hydrotreatment technology is the fixed bed hydrogenation technology in the described step (3), adopt the fixed bed residual oil hydrocatalyst, operational condition is: reaction pressure is 5-35MPa, thermotonus 300-500 ℃, volume space velocity is 0.1-5.0h during liquid
-1, hydrogen to oil volume ratio is 100-5000.
13, according to described residual oil-refining of claim 1 and method for transformation, it is characterized in that the hydrotreatment technology is the fixed bed hydrogenation technology in the described step (3), operational condition is: reaction pressure is 10-20Mpa, and temperature of reaction is 350-450 ℃, and volume space velocity is 0.15-2h during liquid
-1, hydrogen to oil volume ratio is 500-3000.
14, according to described residual oil-refining of claim 1 and method for transformation, it is characterized in that the hydrotreatment technology is the fixed bed hydrogenation technology in the described step (3), comprise at least one fixed-bed reactor or reaction bed, at least filling weight, residuum hydrogenating and metal-eliminating, Hydrobon catalyst in described reactor or the reaction bed, reaction raw materials should be successively with heavily, residuum hydrogenating and metal-eliminating, Hydrobon catalyst contact.
15, according to described residual oil-refining of claim 1 and method for transformation, it is characterized in that catalytic cracking reaction generates in the described step (4) slurry oil after the suspension fine particle that it contains is separated, the hydrogenation reaction system of delivering to described step (3) mixes with described hydrogenating materials and carries out hydrogenation jointly.
16, according to described residual oil-refining of claim 1 and method for transformation, the operational condition that it is characterized in that catalytic cracking unit in the described step (4) is: temperature is 450～600 ℃, agent weight of oil ratio is 2～30, with catalyzer duration of contact be 0.1～15 second, pressure 0.1～0.5Mpa, the catalytic cracking catalyst that is adopted are selected from one or more in silica-alumina catalyst, silica-magnesia catalyst, acid-treated carclazyte and X type, Y type, ZSM-5, M type, the layered molecular sieve cracking catalyst.
17, according to described residual oil-refining of claim 1 and method for transformation, the operational condition that it is characterized in that catalytic cracking unit in the described step (4) is: temperature is 460～550 ℃, agent weight of oil ratio is 2～20, with catalyzer duration of contact be 0.5～5 second, pressure is 0.1～0.5Mpa, and the catalytic cracking catalyst that is adopted is a molecular sieve cracking catalyst.
18,, it is characterized in that described vacuum gas oil enters catalytic cracking unit and further handles according to described residual oil-refining of claim 2 and method for transformation.
19,, it is characterized in that described vacuum gas oil enters the hydrogenation reaction section as the fusion charging and further handles according to described residual oil-refining of claim 3 and method for transformation.
20,, it is characterized in that described vacuum gas oil enters catalytic cracking unit and further handles according to described residual oil-refining of claim 3 and method for transformation.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001231359A CN1152945C (en) | 2000-10-26 | 2000-10-26 | Process for refining and coverting residual oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001231359A CN1152945C (en) | 2000-10-26 | 2000-10-26 | Process for refining and coverting residual oil |
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| Publication Number | Publication Date |
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| CN1351129A true CN1351129A (en) | 2002-05-29 |
| CN1152945C CN1152945C (en) | 2004-06-09 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497548C (en) * | 2002-12-20 | 2009-06-10 | 艾尼股份公司 | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues |
| CN102041045A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | On-stream method of residual oil hydrogenation process |
| CN101161790B (en) * | 2007-10-30 | 2011-07-20 | 徐州工业职业技术学院 | Method for gaining high conversion rate by catalytic hydrogenation of vacuum residue over-critical extraction slag with zeolite molecular sieve |
| CN102311793A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Catalytic cracking material pretreatment method |
| CN113105914A (en) * | 2021-04-22 | 2021-07-13 | 中国石油化工股份有限公司 | Method for producing olefin and aromatic hydrocarbon by processing crude oil and oil refining method |
-
2000
- 2000-10-26 CN CNB001231359A patent/CN1152945C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497548C (en) * | 2002-12-20 | 2009-06-10 | 艾尼股份公司 | Process for the conversion of heavy feedstocks such as heavy crude oils and distillation residues |
| CN101161790B (en) * | 2007-10-30 | 2011-07-20 | 徐州工业职业技术学院 | Method for gaining high conversion rate by catalytic hydrogenation of vacuum residue over-critical extraction slag with zeolite molecular sieve |
| CN102041045A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | On-stream method of residual oil hydrogenation process |
| CN102041045B (en) * | 2009-10-21 | 2014-12-10 | 中国石油化工股份有限公司 | On-stream method of residual oil hydrogenation process |
| CN102311793A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Catalytic cracking material pretreatment method |
| CN113105914A (en) * | 2021-04-22 | 2021-07-13 | 中国石油化工股份有限公司 | Method for producing olefin and aromatic hydrocarbon by processing crude oil and oil refining method |
| CN113105914B (en) * | 2021-04-22 | 2022-05-27 | 中国石油化工股份有限公司 | Method for producing olefin and aromatic hydrocarbon by processing crude oil and oil refining method |
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| Publication number | Publication date |
|---|---|
| CN1152945C (en) | 2004-06-09 |
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